Copolymerization of vinyl monomers with fatty oils, fatty acids, resins and the like



Patented July 1, 1952 COPOLYMERIZATION OF VINYL MONOMERS WITH FATTY OILS, FATTY ACIDS, RESIN S AND THE LIKE Edward C. Haines, Moorestown, N. J assignor to j Geo. D. Wetherill Varnish 00., Inc., Camden;

N. J.,' a corporation of New Jersey No Drawing. Application March 23, 1949,

Serial No. 83,094 J 7 Claims. 1

This invention relates to copolymerization of vinyl monomers with fatty oils, fatty acids, resins and the like for the production of liquid copolymers suitable for use in paints and varnishes and'in'the manufacture of other products.

It is well known that undercertain conditions an alkyd resin, such as glyceryl'phthalate and a fattyoil may be combined in an esterifyingre action with evolution of water and that the resultingester or resin, if normally liquid, may polymerize to form a gel, and'in my prior Patent 2,396,698, granted March 19,, 1946,1'have disclosed-a' process for preparingoil modifi'edalkyd resins of this type and have set forth certain precautions which should be observed to avoid polymerization and hence gelation of the resinous a ester produced.

In accordance with the present invention, how- 5 ever, esterificationdoes not occur and' as' water is excluded from the reacting mass the copolymerization of the starting materials is carried out in an anhydrous system and 'under'condi- V tions such that there results'a c1ear:homogeneous reaction product liquid vat, the reaction tempera ture and having no tendency to form agel; these products, some of which may; solidifytothermoplastic resinous solids at normal. temperature exhibit'numerous desirable properties when dispersed in apsuitable solvent and employed in paint, varnish or the like, while some of the copolymers obtainable in accordance with the invention may be used to advantage in industry otherwise than as coating materials;

Aprincipal object of the invention therefore is the production of clear, non-gelling'copolymers of certain classes or groups of compounds as well as the provision of a novel method adapted for that, Purpose.

A further object is the provision of a novel methodi of.copolymerizing a vinyl compound or the'likewith afatty oil, fatty acid, resin or generally similar material'capable of forming copolymers with the vinyl'compound selected.

Attempts have heretofore been made to produce copolymers' of the natureof, those to which the invention relates and certain processes have met with some success in the laboratory, notably those in which solvents are used as vehicles for the reactants and reaction products and those employing catalysts, either supplied from anin'-- dependent. source or produced internally by first subjecting oneof the reactants, usually an oil, to preliminary partial oxidation resulting according to;on'ej*authorit'y in formation of peroxide, hydroperoxide and epoxy groups which'then act w as catalysts in subsequent copolymerization with a vinyl compound such as styrene.

In accordance with the present invention, however, solvents are not utilized and no catalysts, either external or internal are required, the novel method it'contemplates producing 'copolymers continuously and with desirable properties inherently fixed, thusfrendering the product immediately available for use in industry without further treatment.

It is therefore another object of the "invention to provide a novel method 1 of copolymerizing vinyl compounds and materials copolymerizable therewith to produce directly clear copolymers of the desired properties free of solvents, catalysts or the like.

A further object is to produce with the aid of said method certain copolyme'rs heretofore unknown and unobtainablewhich afford oppor-' tunities for improvement in the paint and varnish industry and in the production of a .wide range of products useful therein and/or in other industries.

A still further objectis to provide a method of I producing initially a seed quantity of, the reactive mass essential to the continuous practice of the principal continuous method contemplated by the invention. j

Other objects, purposes and advantages of the latter will hereinafter more fully appear or will be understood as the following description of a satisfactory manner of practising it proceeds, reference being made by Way of example particularly to copolymerization of, styrene with China-wood oil,'both wellkno'wnproducts readily available in the market in satisfactory degrees of purity, since styrene is deemed typical of the vinyl compounds and China-wood oil 'of 1 the fatty oils which may be copolymerized in accordance with the invention, this oil exemplifyingas well'the resins and fatty'acids'which may be copolymerized withl o like procedures;

In initiating continuous practice of the method. it is essential first to obtain at least a small quantity'of the copolymer'to be produced; this seed material-may be. prepared in" a. batch process, which'while somewh'at more complicated than the continuous one which may be initiated as have notbeen previously'known or of which noexisting supply is'available after the seed material has been produced, 'is' Ifhus' for the production of copolyiners of" styrene and China-wood oil, I may preliminarily prepare at room temperature a mixture of 5 parts by weight of each of these materials, this mixture being hereafter referred to as mixture A.

To 5 parts of China-wood oil heated to 400 F. in a suitable container and in an atmosphere of CO2 to prevent oxidation by atmospheric oxygen I add slowly, at the rate of about 1 part per hour or thereabouts 3 parts of mixture A while keeping the temperature of the mix at about 400-410 F. After this stated quantity has been added, the mass still maintained in an atmosphere of CO2 may be allowed to cool and after -18 hours at room temperature then reheated to about 380 and 2 parts more of mixture A added slowly, at

the rate of about one-third to one-half part per mixture B and one and one-fourth parts of this mixture added slowly to the mass at the rate of 1 part or less per hour, the temperature being maintained at about 380-400 F. At the completion of this addition it may be found the entire mass has gelled, in which case the temperature i increased fairly rapidly to about 560 F., or until the gel is broken down, at which point the mass is cooled rapidly to 420 F., the heating to 560 F. and subsequent cooling to 420 F. together requiring in the aggregate about minutes, that is about 15 minutes for heating and about 5 for cooling.

Thereafter the remaining 2 parts of mixture B are added at the somewhat more rapid rate of about 4 parts per hour and heating is then discontinued. Next, after about 16 hours at room temperature, the mass is again reheated'to about 400 F., and twoand one-half parts of mixture A are slowly added at the rate of about 1 part or less per hour,or about 3 hours for the entire addition. Four parts of the mass are now removed, cooled rapidly to room temperature and 1 part of styrene monomer stirred into it, forming mixture C the entire quantity of'which is now added at .the rate of about 2 parts per hour to the mass at 400-420 F. About one-half hour later heating is again discontinued and the resulting mass, containing in this instance about 91 /2 ofstyrene-China-wood oil copolymer allowed to attain room temperature.

This material, which is homogeneous, substantially clear and transparent, color 3 on'the Helligeklett scale with acid number 4.78 and viscosity Z6 plus 4 bubbles on the Gardner-Holdt scale, is substantially identical with the product of my continuous process which may now be commenced using the said material as a seed or vehicle for the continuous reaction.

In initiating the operation ofthe latter a convenient quantity of this seed material is heated to and maintained at a temperature preferably of about 400 F. in a suitable container while'there is being slowly and continuously added to it a mixture comprising, for example, 2 parts Chinawood oil and 1 part styrene monomer at a rate of addition desirably such that the proportion of unreacted material to the entire mass-is kept low and the concentration of unreacted styrene'in the latter is therefore always still lower. Consequently after the mass in the container has attained a sufficient volume, it maybe withdrawn at substantially the same rate as the oil-styrene mix is being added so as to maintain it thereafter at a substantially constant volume. When the outlet from the container is fairly remote from the point at which the unreacted oil-styrene mix i added little if any of the latter is withdrawn as such and substantially all the added material enters into the copolymerization reaction before reaching the discharge port of the container in which a transit time of about 12 hours is desirably maintained. However, to insure complete copolymer formation and combine any unreacted styrene possibly retained in the product the latter may be carried through a second container preferably maintained at about 400 F. in a transit time of about 3 hours more or less while a relatively inert gas such as CO2 or nitrogen is bubbled through the mass to effect its constant agitation and maintain it in an inert atmosphere to inhibit its oxidation by atmospheric oxygen.

The temperature at which the copolymerization is maintained is preferably just suflicient to cause the reaction to proceed at a moderate rate and is therefore dependent somewhat upon thespecific ingredients entering into the reaction and the proportions thereof supplied. Thus when styrene and linseed oil are copolymerized in accordance with the invention at temperaturesas low as 350 F. the reaction proceeds relatively slowly but otherwise satisfactorily whereas when the charging materials contain di-vinyl benzene or a bodied wood oil it is usually necessary to maintain a temperature of about 450 F. or higher in the mass to effect adequate copolymerization.

Moreover while in the example cited 2 parts of China-wood oil and 1- part of styrene monomer formed the charging mixture, larger proportions of China-wood oil up to 90 %-95 thereof or smaller proportions as low as 10%-20% with theremainder styrene may be employed to produce correspondingly difierent copolymers, but when the proportion of styrene is less than about 33%% the copolymers may exhibit gelling tendencies on prolonged heating. More specifically, a mixture of China-wood oil and styrene monomer containing 90% of the former and 10% of the latter c0- polymerized at a temperature of about 400 F. with a turnover time of about 5 hours results in a clear fluid copolymer having a viscosity of 27,

' an acid number of 3.5 and a color of 13 (Gardner) with a non-volatile content of 98.5%. This product is useful in the manufacture of varnishes under circumstances in which, China-wood oil alone cannot satisfactorily be employed on accountof its rapid rate of bodying. Thus an excellent 20 gal. varnish may be made with-it and a maleic modified rosin ester, although the latter cannot be combined with raw China-wood oil to make a useful product. v l

When there are employed in the initial feed relatively smaller proportions of China-wood oil, for example about 20%, at somewhat lower temperatures in the reacting mass, a clear resin is produced having a non-volatile content of 96.4 and acid number 3.66 which is solid at room temperature and in a solution in mineral spirits has a viscosity of. 46.3 poises and a color of 13;

in a solution in-xylol a precipitate may be formed Obtained by initially heating the oil to 450 F. and y .maintami eit t h t em e atu i9 1 ab t, ":r'ninutes'.;then chilling it with'a' suincientguantity 'rawbirtb bring to consist'enc" 'to about 6.0

'copolymerized with; about an equal quantity of styrene mo'norner ata temperature of :400'1130 429 F. with'turnov'er time of about 25 hours, a clear viscous copol ymelr isiqbtainedhaving nonvolatile content 9'6.5%;'visoosity 23.5 poises', acid' number 3.35 and colorl4'.

' Oils other than those to'which specific refcerence has been made may of course be employed "and 'for the styrene'in the feed mixture di-vinyl benzene maybe substituted in whole orinpart, Thus a" copolymerization feed comprising 50% distilled tall oil, 40% styrene and 10% of a m ix-' ture consisting of 40% vdi-vinyl'benzene and 60% j ethyl styrene, in a pre-formed wpolymer made from the same ingredients, at atemperatureof 450 F. and turnover time of about 13 hours, proj'duced a copolymer of nonvola tile content'93.8%

acid number 100, viscosity 36.2 poises at 80% solids in mineral spirits andcolor 14.

While I have herein suggested ranges of proportions of certain ingredients which may be 6111-: ployed in accordance with the invention foriproducing copolymers and which include, for example, chinaw oodoil-styrene mixtures containbutjiiery little" of one and correspondingly more of the other, as a. practical'matter copoly mers made using these proportions may be of little, if any, commercial valueythosemade from mixtures containing less than about30% of the oil show progressively decreasing compatibility with drying oils and petroleum solventsas the proportion of China woodoil is decreasedjbelow 30% while those made from mixtures containing 'inorethan 90% of the oil, although clear products appearto have but relatively limited practical usefulness for economic reasons.

Substantially any of the copolymers produced in accordance with the invention maybe used as a base for paints or varnishes, havingfproperties superior to corresponding copolyrners made from the same starting materials but copolymerized or attempted to' be copolymerized with the aid of catalysts, solvents or the like; moreover they differ markedly"iirphysicalproperties as well as in "chemical characteristics froin the alkydresinous products produced man esterification reaction in acgordancewith my said prior patent, since while the procedures employed therein and inthe present method are in certain-aspects mechanically analogous, in the latter esterification', essential in the patented method, is wholly avoided and the' only reaction occurring as ;far as can be ascertained byknowntesting methods 115 one of copolymerization inwhich the molecules A of the vinyl compound'and the oil or resinous modifying agent instead o f reacting only with themselves to form a rnixture of individual copolyniersseem to react together to form? the co-' polymer as a clearly distinct compound inheriting some of the characteristics of each of the parent compounds but unlike either of them or amixyeaeaendfi ii a i e a mai l ein if bo The acid number of this ii' oaamen ture or their individjiial polymers and wholly I distinct from p em re; of any known esterifi'cationre'a'ctions' which "maybe entered-into "by eitherlf 3 11.: 5 Thus where 1 part glyceryl phthalate and '2 parts China-wood oil are subjected-w est e mth'e inaiiner dsciibea'in saidpa ntthe 'p duct is an-dime fid resinhavingi "riur'riber'ffi i which was' reduced-' to=fl33 heat 1 t ams a "Fl r* q m iui setWl l t pre il tsia r d gel-i I? 7' i if A l m o i 1: 1p Styren and. ar China-wood oil produced in accordance with the n present method however and having a""'su tan- Mitially lower initial number ma ibe ,In'aini dfl 45 indefin i' ithd v l any, tendency to g eland'withbut .appr

; ilcfienin' sa ifiinu b :f

. Itis ja coldi lyfip ni th P s t although involving mechanical steps" similar to generally corresponding on I I y said patented method produces different results because it proceeds by copolymerizatijon of the materials whereas the patented methddproceds by polyesterificationl '1 Continuous i- ,e 'peiym riz a tion in accordance with the present meth od Proceeds most satisfactorily when an initi' bulk Q fihe reaction mixture is fpreiornied cop mer of substantially the 1 same materials andpropor- 3 tionsas the feed and'the feed'of newfmat'erials equivalent is lrnaintainedat' a rate substantiall I t jf hei a c ol ri t on' vhrby I'th propo1*tion of v copolymeriz ejd to unreactle d materials is maintained substantially constant/ Thus 35 monomer in the mass atany'time jor'erianiple styrene, the rate of copolyme remains 'is w KC (X X wher e Kc' is constant. :Xis less than unity andprefer'ably '1 noi; greater "than about 0.10, X i always less thaiiX and en xiii-S reduced below X? becomes prog "sslvly still smaller so thateve'n 'thouglfKffiiayjbe ti on of polystyrene through interpolyni of styrene, and sustainscopolymeriiatio' 7 major ii not the sole reaction inthe mass? Con- 'sequentlyany tendency of'the vinylco'mpoundto ipolyxnerize independently of the, other ingredient fisfinhibited by' the' dominant copolynierization o tendency while the presence in the re aotion mass rew; a small quantity of free v'i'n'yi ebmboimd at any time moreover deters "its vola despite s normal yolatilit'y' at; the temp .Ilmploy'e' i" i :1

n: will be appr ciated thatthe procedure herein described "for producingfan initialfseed quantity of the desired cop o lyrner by" a batchv process is not necessary ,each time continuous fgproduction' of the 'copolyxner, is initiatedzprob 'vided there is available for use'a sufncient quanv tity of the latter furthermore it is obvious zfrom hat been s'a regarding the desiredrelation 1 J 'etween rate,,-of-..feed and-volume of the reacting fi mi e g c n -mass iserequired,

volume 'require'd'to give satisfactory yield.

Moreover, while I haveldescribed in' considerable detail one method I have followed for inlii X representsjthe" concentration f ofthei vinyl iz ialtlion I ass that to prodnce a high rate of yield ai'cor P t i I imey, ree be eer b' q from an iniially" relatively. small quantity i th epol purpose.

.f It. will also be apparent that while I have product of the batch method, while equally useful with theproduct of the continuous method, is of course more difiicult to obtain and the said or any other batch method will therefore ordinarily be employed as a starting point for the continuous method only when insufiicient of the desired copolymer is otherwise available for the herein described the practice of the invention in the production of copolymers particularly .of styrene and China-wood oil these materials are merely exemplary of the classes of compounds materials in their respective classes. Moreover as resinous monomers respond to treatment in accordance with the invention similarly to China-wood oil and other fatty oils, they may be deemed for purposes of the invention in the same-general class as the latter and the probedurespecifically described therefore exemplifiescopolymerization of a vinyl compound with either a fatty oil or with a resinous monomer.

7 Thus among other materials represented herein byChina-wood oil may be mentioned oiticica oil, tall oil, rosin and polycarboxylic-poly alcohol resins and derivatives of these latter mate- 'rials and in some instances slight modifications of procedure may be desirable when one of these is employed. v

Furthermore, divinyl benzene as indicated in one example maybe contained in a mixture of vinyl compounds which may be employed although it usually requires somewhat higher temperatures than styrene, up to about 450 F.

inthe reaction mass, and other vinyl compounds substituted for or mixed with styrene in the feed may require similar simple modifications in procedure. p

fit is therefore to be understood the invention isnotto be deemed as limited or confined in any .way to the specific disclosure herein recited as wide latitude in the selection ofstarting materials'is afi'orded to enable the production of numerous specifically different copolymers adapted for various uses while changes and modifications in the specific steps in the method itself will readily occur.to those skilled in the art and may be made if desired without departing from the spirit and scope of the invention as defined in the appended claims.

Having thus described my invention, I claim and'desire to protect by Letters Patent of the United-States: V g

1 ii The method of producing a copolymer of styrene and a monomer selected from the group consisting of China-wood oil, oiticica oil, tall oil monomer and the copolymer, that ingredient of the mixture entering less readily than the other 'may, be devised or changes and modifications t introduced in the one I have described. The end tov which they belong and like procedures may be employed for obtaining copolymers of other into a copolymerization reaction with such other being present in the mass in relation to such other in proportion larger than the proportion thereof entering into the reaction, continuously withdrawing from the mass a volume of fluid substantially equivalent to the volume of said mixture being added thereto and consisting substantially of the copolymer with not in excess of 10% of unpolymerized styrene and said monomer.

2. The method defined in claim 1- including the step of maintaining the fiuid withdrawn from the reacting mass at a temperature of approximately 400 F. for approximately 3 hours subsequent to its withdrawal while agitating it in the presence of a gas inert with respect thereto.

3. The method as defined in claim 1 in which the reacting mass is maintained at a temperature between 350 F. and 450 F.

4. The method defined in claim 1 in which the volume of the reacting mass is maintained at a ratio to the mixture being added thereto such that at no time during the progress of the reaction the unpolymerized portion of the said mixture comprises a proportion of the mass in excess of 10% thereof by weight.

5. The method defined in claim 1 in which the said mixture is fed to the reacting mass and the material of the latter withdrawn at a rate such that a volume of the mixture substantially equal to that of the mass is fed to the latter in a period of approximately 12 hours.

6. A method of producing a chemically homogeneous copolymer of styrene and a monomeric substance from the group consisting of Chinawood oil, oiticica oil, tall oil and rosin which comprises the steps of maintaining a mass of a copolymer of said materials at a temperature substantially above its temperature of solidification, supplying said. materials thereto in quantities such that in the reaction mixture the less reac tive of said materials is present in proportion sufficiently greater relatively to the other material than the proportion relatively thereto at which it enters into copolymerization reaction therewith that copolymerization predominates in the reacting mass and excludes homopolymerization of the more reactive material, said relative concentrations of the monomeric materials automatically maintaining in the mass a concentration of total uncopolymerized materials not in excess of 10%.

7. The method defined in claim 6 in which the reactants are styrene and China-wood oil.

EDWARD C. HAINES.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name 7 a Date 1,975,959 Lawson et a1. Oct. 9, 1934 7 2,363,951 Fiken'tschev Nov. 28, 1944 2,396,698 Haines Mar. 19, 1946 2,451,435 Elwell et a1 Oct. 12, 1948 2,468,748 Griess' et al. ,May 3, 1949 2,496,384 De Nie Feb. 7, i950 FOREIGN PATENTS Number Country Date 573,335 Great Britain Dec. 7, i945 

1. THE METHOD OF PRODUCING A COPOLYMER OF STYRENE AND A MONOMER SELECTED FROM THE GROUP CONSISTING OF CHINA-WOOD OIL, OITICICA OIL, TAIL OIL AND ROSIN WHICH COMPRISES THE STEPS OF CONTINUOUSLY ADDING TO A MASS OF THE COPOLYMER MAINTAINED AT A TEMPERATURE SUBSTANTIALLY ABOVE ITS TEMPERATURE OF SOLIDIFICATION, A MIXTURE CONSISTING OF STYRENE AND SAID MONOMER IN PROPORTIONS SUCH AS TO MAINTAIN IN THE MASS A SUBSTANTIALLY CONTANT RATIO BETWEEN THE STYRENE, SAID MONOMER AND THE COPOLYMER, THAT INGREDIENT OF THE MIXTURE ENTERING LESS READILY THAN THE OTHER INTO A COPOLYMERIZATION REACTION WITH SUCH OTHER BEING PRESENT IN THE MASS IN RELATION TO SUCH OTHER IN PROPORTION LARGER THAN THE PROPORTION THEREOF ENTERING INTO THE REACTION, CONTINUOUSLY WITHDRAWING FROM THE MASS A VOLUME OF FLUID SUBSTANTIALLY EQUIVALENT TO THE VOLUME OF SAID MIXTURE BEING ADDED THERETO AND CONSISTING SUBSTANTAILLY OF THE COPOLYMER WITH NOT IN EXCESS OF 10% OF UNPOLYMERIZED STYRENE AND SAID MONMER. 